Antistripping agents for asphalts



Patented Dec. 30, 1952 UNITED. STATES amass n I,

mrsrmrtmt mm i on ssrfist'rs Eo'uis A; Mikeska; westfield N; 1;,- assignor to Standard Gil Deie ration of Delaware liiixment Company, acorpo- No Drawing. iipii cationfloy'einlief 23; E48,

Sriai'No. 61,735 r 6 clai s 1 object of this invention isaeompositj'n-of matter odnipdsed of asphalt and the free am to obtain. A more readily available and more economic-a1 source of this t pe of aikyl' halide n tei'n ediates was desired for this purpose. According to this invention, 7 effective antistripping addition agents for asphalts can bf 'prepared by the condensation of various types fOf alkyl; halides with polyalkylene bolyariiifies'fsudh as ethylene diamine', diethylene triamine, triethylene tetra/mine, and mixtures thereof; It should be understood that wherever th condensation srcqaetwasears this swims:- tion; it is intended to mean the free amin bQ-s'e" treat the reaotidiimixtuie direotly W strong base sum as sodium hydroxide and there after isolate the free amine base; One very good method of preparing the desired effective anti-stripping addition agents is based orr tr ie oondensation of highmolecular weigh kyl' halides with ethylene di'afflii'ie or with so e other poiyal yiene poylarnines. The ainiiie droh-aiide salts thusobtained may beujsed assu or they may be converted, by" neutralizatio the free-bases which may b'eus'ed as" such or may begin turn eonve'rted intoothefisalts, fifefe ganic cartoxylid aoia salts or sfilioni prior to their blending with asishsits. The" products, whenprofierly prepared, ofisisfi primafily of mono alkyl-ates ethylene diaihfi'ieof polyethylene polyami-nes; though polyalkylated products are also present. 7

alkyl l i'alids are fiartiulai 'iii Valuati'e for use preparing t ese improved anti-- i stripping agents may contain" front l0' to 24 car boriatoms. Lower moie ularweight prodifot'sglye poor results. The halide atom srrduidf be: located his prim aryorseconciar posit on. The ternaryhaiids give inferior reaetioii' israduetsis they" tend to undergo dehydrol ialogenat'ion rather than condensation when treated with the polyamines.

Various other substituents may also be present.

These include such groups as phenyl, phenoxy, alkyl substituted phen'yl', hydroxy, alkoxy, mewcapto', alkyl substituted mercapto, and various others. I T eir-arrangement in the molesule' is not partiulalilycritieal. However, the halide atom to be reacted with the: polyamine must be attached These. products may obviously be prepared by other known synthetic reactions and the inven tiit fidt intended in be limited to any parti'ou lar madeof nr'o'ducing the usefulcompounds.-

ri afi the products thus obtained are highly effeotive as afiti s'trifiiiirig addition agents for as nal ts may be seen from the fol-lowing detailed exazhnl's and' the evaluation data given below.

A. condensation of high, molecular weight unsub stituted alkyl halides and gfiolyallcylene poly-- amines EXAMPLEI dedSI bromi e byhatifiggaif summons minors q; the: two mgreuiens at 140 0'. r one he The am ne fiydrobrormde thus obta eawas (So verted into the free base by treating the hydro bromide With a slight, excess" pf sodiurfi hydroxide. The free amine base was obtained as' a yiscoiisyellow oil. It's effetiveness as an asphalt antistripping addition agent may be seen froriith'e evaiuafiori data given bel'ow. Trap -i"ool";" contain: iiig 2 water afid,6% asphalt out back Was us d the" evamatidn. Equimolarpfonortions of oleifd acid and the free amine obtained by the above de: scribed procedure were mixed and the resulting salt product likewise tested as; an'asphalt antistripping agent.

' fiesistanoeto Stripping After I v B. Condensation of aZkoxy-hydroxy alkyl halides" and polyalkylene polyamines Products containing primary chloride groups can be readily prepared from-alcoholsby condensing the latter with epichlorhydrin in the presence of an appropriate catalyst. On treat ing the halogenated products thus obtained by this condensation with ammonia or with polyalkylene polyamides, such as ethylene diamine, amino derivatives are thus obtained which are highly effective as asphalt addition agents.

' noon The chemical equations shown above probably represent the general nature of the reactions taking place. It is quite probable, however, that a mixture of reaction products is obtained. Various types of alcohols may be used for the purpose indi-'- cated above, some of which are listed below:

- 1. Straight chain alcohols such as lauryl alcohol, cetyl alcohol, octadecyl alcohol, etc. Mixtures of such alcohols such as the alcoholic mixture derived from the reduction of coconut oil acids and which contain C12 and higher and lower alcohols are also useful. One such product is called lorol alcohol.

2. Branched chain alcohols such asare obtained on applying the 0x0 reaction (where carbon monoxide and olefins are condensed to produce aldehydes which are then reduced to alcohols) to such olefins as di-, tri-, or tetra=isobutyl ene, polypropylenes,or various polymers obtained in the process of polymerizing 'low molecular weight olefins. V

3. The alcohols obtained on hydration of di-, tri-, or tetra-cyclopentadiene.

- 4'. Alcohols such as are obtainable from cracked waxes.

That the products obtained as outlined above make highly efiective-asphalt anti-stripping or wetting agents. can be seen from the following examples.

OHgOH EXAIVIPLE II (B-aminoethylamzno) -hydromypropz/Z nonadecyl ether Nonadecyl alcohol which was obtained from Cm polypropylene by the Oxo reaction was condensed with epichlorhydrin in the presence of boron fluoride in the usual manner. Without any further purification the condensate was heated for 1 hour at 130-140 C., with a slight excess of ethylene diamine. The hydrochloride was con-' verted into the free base by treating the former with a slight excess of sodium hydroxide. The amine was obtained as a viscous yellow oil. Without any further purification the product was evaluated as an asphalt wetting agent. Trap-rock containing 2% water and 6% asphalt cut-back 4 was used. The salt of the amine with oleic acid was prepared by mixing equimolar quantities of the free base and salt. This product was likewise evaluated as an asphalt wetting agent.

Resistanfxefgo Stripping p Percent Product Tested Gone. in

. Asphalt Ability 0 Hr. 1 Hr. 2 Hrs.

Cure Cure Cure C. Condensation of p-haloethyZ-alkyl sulfides and polyalkylene polyamines Efiective addition agents can also be prepared by condensing B-chloroethyl-alkyl-sulfides with polyethylene polyamines such as ethylene diamine. Other polyalkylene polyamines may also be used.

The alkyl chain in the B-chloroethyl-alkyl sul-. fide may be either straight chain or branched chain, though a straight chain seems to be somewhat preferable.

As may be seen from the evaluation data given below, although the free bases are highly potent as asphalt addition agents, certain carboxylic acid salts of the same are even more active.

The B-chloroethyl alkyl-sulfides may 'be' prepared in various ways,-as for example by condensing a mercaptan with an alkylene oxide and l by then halogenating the resulting product in any of the well known ways. 1

'- CnHzs (Econ, cleanser-1,011,011

cnHtscmcmon P01,s s j CliHssSCHzCHzCl PO01: +301 A more convenient method for the preparation of the ,B-chloroethyl sulfidesconsists of treating an alkali salt of a mercaptan'with an excess of ethylene chloride in an alcoholic solution.

Then-by heating the chloroalkyl alkyl thioether thus obtained' with ethylene diamine under atmospheric pressure, a monoor poly-substituted ethylene diamine derivative is'obtained.

EXAMPLE III A round bottom flask equipped with a return condenser, was charged with 16.2 gms. (0.27 mol) of ethylene diamine and 23.7gms. (.0896 mol) of s 4 chloroethyl lorolsulfide, C12H25SCH2CH2C1. The mixture was then heated at to C. for 1 hours. The mixture was non-homogene5 ous to start with and continued tobe unm nout-the. reaction. The reaction product. was. then. cooled; poured into water, neutralized with .a slight excess of dilute sodium hydroxide. and extractedwith ether. The extract was dried over sodium sulfate and the solvent was removed on the steam bath. The residue consisted of 23 gms. of light. colored viscous oil. which contained 7.22%initrogen, 1 0.57 sulfur and. only a. trace. of organic chlorine. Without any further purification the. product was blended with asphaltcutback in the concentrations indicated below, and evaluated as an asphalt. addition agent, using New Jersey traprock: as the other component of the test material. The results of the test are. given below. 6% as. the asphalt cutback and 94% of; the rock aggregate was used in the tests. The tall; 011 saltv of the base was also tested and found to be satisfactory asv an anti-stripping agent.

..:Traproclr+2%' 11 P t ItQSiSBIIGG to Strip- .ercen ping er- Mixing Product Cone. in

Asphalt Ability v 0 Hr.v 1 HI. 2 Hrs. Cure Cure l Cure Free Basesr 2.0 100 v 100 100 100 D0.-. l. 0- 95+ 95+ 95+ 100 Do... O. 5 95 9,5 100. 100 D0. 0. 90+ 95' 100 Tallaoilsalt 23.0 100 100 100. 100

,Do 1.0 95+ 100 100. BIL-.. 0. 6 25 95+ no- 0.25 90 5 95+; 95+ Asphalt cutba additive 5 10 20 EXAMPLE IV- N-fl terticrpoctylthioethyl ethylene diamine The intermediate tertiaryoctyl-p-chloroethyl sulfide, was prepared in. the following manner:

To an Erlenmeyer flask containing 200 ml. of absolute ethyl alcohol was added 27 gms. (0.5 mol) of pure sodium methoxide and 73 gms. (0.5 mol) of" a tertiaryoctyl mercaptan. This solution was then added slowly, with rapid stirring, to 198' gms. (2 mols) of ethylene chloride. The reactionf'was rapid and the temperature rose spontaneously to a point where the reaction mixture began to reflux. When all the mercaptide had been added, the heating and stirring was continued for additional four hours. The reaction mixture was then cooled and filtered in order to remove the sodium chloride formed and the filtrate was evaporated to a small volume on the steam bath.

The. residue was taken up with water, acidified with concentrated hydrochloric acid and extracted with ether. The extract was washed. dried over sodium sulfate, and the solvent was finally removed on the steam bath. The residual- Oil was then distilled under 20 mm. pressure. Practically-all the productsdistilled at1126-130 C. The distillate may be designated asproduct A.

The following procedure was used in preparing the desired ethylene diamine derivative:

A round bottom flask equipped with a return condenser and a thermometer, was charged with 13.8 gms. (0.23 mol). of ethylene diamine and .15.6gms.-(0.075 mol) of the above described prodot A. The mixture was then refluxed at C. for 1 /2 hours.

The reaction mixture was then poured into a little water, treated with a slight excess of sodium hydroxide, and extracted with ether. The extract was dried over sodium sulfate. and filtered.

On removal of the ether on the steam bath, 15.5

.of viscous. yellow oil were obtained. With 75-;

out any further purification, the product. was evaluated as an asphalt wetting addition agent in the same manner as described in Example IV.

N p-tertidrydodecylthioethyl ethylene diamine The above indicated dodecyl derivative was prepared in the same way as was described for the tertiary octyl derivative in the previous experiment. This meant simply that equimolecular proportions of tertiary-dodecyl mercaptan was substituted for the tertiary octyl mercaptan of the preceding experiment. As in the previous experiment, the final product was obtained as a viscous yellow oil. Evaluation data for the N-fltertiarydodecylthioethyl ethylene diamine are given below:

Traprock+2% Hi0- P t 38513132106 to Stripcrccn lfixin ping er- Product Gone. in g Asphalt Ablmy 0 Hr. 1 Hr. 2 Hrs. Cure Cure Cure Free base 2. 0 100 95 100 100 D0 1.0 95+ 50 90 90+ D0 0.5 95 I5 35 76 Do 0.25 90 5 15 50 From the data it may be seen that the product was active as an asphalt wetting addition agent.

D. Condensation of alkylphen yl chloroallcyl ethers and polyethylene poly amines Highly eifective asphalt addition agents can likewise be prepared by condensing alkylphenylchloroalkyl others with polyalkylene polyamines such as ethylene diamine.

s-Chloroalkyl-phenyl ethers, such as react readily with,, for example, ethylene diamine on heating under atmospheric pressure to give salts of the amine derivatives:

(3331 0112011101 mNcmoruNH, 1

0811.100 CHzCHgNHCH CH,NH|.H-Cl

On neutralization with alkali, the free amines are obtained. The bases as such or in. the form of'carboxylic or sulfonic acid salts make excellent" wetting agents when added to asphalts. Salts; of monoalkyl sulfates (ROSOaH) or mono or di esters of phosphoric acid may also be used. The effectiveness of the products of this nature may be-seen from the following examples:

EXAMPLE Vi .6. Sewarflask equipped with a stirrer and a reflux condenser was charged'with 56.8 g.- (0.2 mol), of tertiary octylphenyl-fl-chloroethyl ether,

and 12 gms of anhydrous ethylene diamine. The mixture'was then heated for one hour at 150- 160 C., whereupon it was cooled and poured into water. 'A slight excess of dilute sodium hydroxide was then added and the mixture was extracted with ether. .The ether extract was then dried over sodium sulfate and filtered. The filtrate was evaporated to dryness on the steam bath.

The residue consisted of 60 gms. of yellow viscous oilwhich was found to be highly effective as an asphalt addition agent as may be seen from the evaluation data given below:

The stripping tests were run on 6% of rapid curing asphalt cutback type 2, and 94% of wet (2% H2O) New Jersey trap rock. The asphalt cutback conformed to the AS-TM specification D597-46;

'lraprock+2% H2O- Resistsi rtice to Strip- Percent pingA er- Product Gone. in Q Asphalt- A OHrs. lHr. 2Hrs.

Cure Gun Cure I Free Base 2.0 100 100 100 100 Do 1.0 95+ 95+- 100 100 0.5 95+ 55 100 100 0. 25 9O 10 95+ 100' 2. 100 95+ 100 100 1.0 95+ 35 90 100 0.5 90 5 50 100 0. 25 85 O 20 9O "Alkyl phenols can likewise be condensed with epichlorhydrin and by then reacting the resulting chloropropylphenyl ethers with ethylene diamine or other polyethylene polyamines, highly active asphalt wetting addition agents are obtained.

was charged with 103 gms. (0.5 mol) of freshly distilled tertiaryoctylphenol, 200 ml. chloroformand 5 ml..of boron fluoride-ether complex (45%- The dropping funnel wash charged with. 46.3 gms. (0.5 mol) of epichlorhydrin. The epi-: chlorhydrin was then added to the reactor drop. by drop with rapid stirring and sufficient cooling. to keep the reaction temperature between BFs).

C. and C. When all the chlorhydrin had been.

added, the mixture was stirred at roomtempera:

ture for 1 hours.

On completion of the reaction, the reactor ten; tents were poured into 300 ml. of water and the."

solution was extracted with chloroform, The ex-.

tract was then washed with sodium bicarbonate solution and finally dried over sodium sulfate; On removal of the chloroform the residue was analyzed without any further purification:

Found: C: 68.00; H=9.37; (31:11.50; acetyl No.=187.3

Cale: 0:68.34; H=9.38; (31:12.00; acetyl No.=187.6

This intermediate was used in preparing the desired ethylene diamine derivative.

A round bottom flask equipped with a return condenser and a thermometer, was charged with 44.8 gms. (0.15 mol) of the tertiaryoctylphenyl washed first with a little dilute sodium hydroxide solution and then with water, whereupon it was dried over sodium sulfate. The solution was then' filtered and the chloroform was removed on'the steam bath. The residue, after the removal of BOOK 12 112011201 ROOom HwHmmm onion In most cases the reaction with ethylene diamine or with other polyethylene polyamines, can be carried out by merely refluxing a mixtureof the two ingredients under atmospheric pressure. The free bases areobtained from the hydrochlorides by neutralization with alkali. Carboxylic and sulfonic acid salts of the free amine products are also highly active as asphalt addition agents, particularly when used on basic rock aggregate such as limestone.

For purposes of illustration the condensations of tertiary octylphenol with epichlorhydrin and of tertiaryoctylphenyl-chloropropyl ether with ethylene diamine are described below. .Evaluation data on the diamine derivatives are also given. I

EXAMPLE VII TertiaryOctgZphenoxy-hydroxypropyl ethylene diamine A 3-way flask equipped with a stirrer, a return condenser, a dropping funneland a thermometer,

the solvent, consisted of 27.5 gms. of yellow viscous oil.

tithout any further purification the oil was evaluated as an asphalt addition agent in the concentrations indicated below. New Jersey traprock and rapid curing asphalt cutback; type 2, were used in the tests, The asphalt and traprock were used in the ratio of 6% asphalt cutback blend and 94% traprock.

, E. Condensation of arylalicyl halides and poly- In general, similar results may be obtained by condensing alkylated aromatics with formaldehyde in the presence of hydrogen chloride and by then condensing the chloromethylated aromatics with polyalkylene diamines.

' The reactions involved may be illustrated in the chemical equations given below:

The mixture was then cooled, poured into water and extracted with ether. The extract was Washed several times with water and then dried over sodium sulfate. 3

On removal of the ether on the steam bath, a residue consisting of 246 gms. of yellow oil was obtained. This residue may be designated as product B. That the product contained slightly more than one chloromethyl group per molecule of substance may be seen from the analysis given below.

Found: 0:73.04; H:9.03 (11:18:54 C11H15'C1, Cale: 0:72.33; H=8.33; 01:13.96

This product B, whose preparation is described above, was condensed with ethylene diamine as described below: 1

A 3-way flask fitted with a stirrer, a returncondenser, a thermometer, and a droppin funnel was charged with gms. (0.75 mole) of ethylened-iamine, while the dropping funnel was charged with 45.6 gms. (0.25 mole) of product B described in the preceding experiment. The chloride was added to the diamine little by little OCizHuCl HQNCHQCHINH: --i OCnHuNHCHzCHgNHaHC] OC H NH CH CH NH II C1 NBOH @CnHuNHCH CHaNH: NaCl CDHIQO 01120 HCl 011 00mm Inc 0110011101 q-nmomcnmm CQHNOCHZNHCHzCHzNHaHCI cHwC 0HmHoniomNHtHo1+Nao11 CzHuQOHaNHCHzCHzNHz+ NaCl The free bases as well as sulfonic or carboxylic acid salts of the bases make effective addition agents for improving the adhesivity of asphalts to the rock aggregate.

Any alkylated aromatic such as various fractions of aromatic petroleum distillates may also be used for this purpose. Synthetic alkylated aromatics are equally useful.

Methods are described below .for the preparation of the intermediates as well as of some of the final products.

F. Condensation of polyalkylmylalkyl halides and. ethylene diamine EXAMPLE VIII Tetramethylbenzyl ethylene diamine A petroleum distillate consisting primarily of a mixture of tetramethyl benzenes was chloromethylated by condensation with formaldehyde and hydrogen chloride in the following manner:

A 3-way flask fitted with a stirrer, a return condenser, a thermometer, and an inlet tube for the introduction of hydrogen chloride, was charged with 201 gms. (1.5 moles) of crude tetramethyl benzenes, 45 gms. (1.5 moles) of trioxymethylene, and ml. of 85% phosphoric acid. Rapid stream of hydrogen chloride was then passed through the mixture and the temperature was raised to 80 C. This mixture was rapidly stirred throughout the reaction. Then, while maintaining the temperature at 80 C. the stirring and passage of the hydrogen chloride Was continued for four hours,

with rapid stirring and sufiicient cooling to keep the reaction temperature below 60 C. The mixture was then heated for 1 hr. at C.

On completion of the reaction, the product was poured into water and extracted with ether after neutralization with 25% sodium hydroxide. The extract was washed and finally dried over sodium sulfate. On removal of the ether on the steam bath the reaction product was obtained as a yellow viscous oil, weighing 38.8 gms. Without any further purification, the product was evaluated as an asphalt addition agent. I Traprock containing. 2% water was used as thero'ck aggregate. The ratio of the two ingredients used in the tests was 6% of the asphalt blend to 94% of the rock aggregate. That the product was highly active as an asphalt addition agent may be seen from the data given below:

pared by condensing crude trimethyl benzene with formaldehyde and hydrogen chloride in a manner exactly analogous to the method used in the condensation of tetramethyl benzene with formaldehyde and hydrogen chloride described in the preceding experiment. In this case the chloromethyl derivative so produced was found to contain 17.65% chlorine. For convenience this material may be designated as product C.

Product C was condensed with ethylene diamine and the reaction product isolated in exactly the same way as was described for the preparation of the diamine in the preceding experiment. The finished product was obtained as a yellow viscous oil, which was evaluated as an asphalt addition agent in the manner described above for the corresponding tetramethyl deriva- 2. In this case the trimethyl chloromethyl benzene was prepared by direct chlorination of tetramethyl benzene. The procedure was as follows:

A small reaction bottle was charged with '71 gm. of crude tetramethyl benzene and 3 gms. of

phosphorus trichloride. A rapid stream of chlorine was then passed through the liquid at about 7 derivative with ethylene diamine was carried out I exactly as described for similar condensations in the preceding examples. The finished diamine was obtained as a dark red liquid which still contained some chlorine. The presence of the chlorine did not seem to interfere with the activity of the base as may be seen from the evaluation data given below. 1

What is claimed:

'1. An improved bituminous bonding composi. tion comprising a mixture of asphalt and at least one anti-strippin addition agent selected from the group consisting of the free amine base and salts of the free amine base of the condensation product of ethylene diamine and an alkylthio substituted alkyl halide, said alkylthio substituted alkyl halide containing only carbon, hydrogen, oxygen, sulfur and halogenelements, and having an alkyl radical of 10 to 24 carbon atoms.

2. The composition defined by claim 1, wherein the'sa-id alkylthio substituted alkyl halide is B haloethyl-alkyl sulphide. I

\ 3. The composition defined by claim 2, wherein the said [i-haloethyl-alkyl sulphide is fi-chloroethyl-alkyl sulphide. v

4. The composition defined by claim 2, wherein the said fi-halo-ethyl-alkyl sulphide is [3-011101'0- ethyl-loro-lsulfide.

5. The composition defined by claim 2, wherein the said B-haloethyl-alkyl sulphide is tertiaryoctyl-B-chloroethyl sulphide.

6. Thecomposition defined-by claim 1, wherein the said B-haloethyl-alkyl sulphide is, tertiarydodecyl-c-chloroethyl sulphide.

LOUIS A. MIKESKAJ REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,191,295 Dohse et a1 Feb. 20, 1940 I 2,246,524 Kyrides June 24, 1941 2,378,235 Miles June 12, 1945 2,461,971 Fischer Feb. 15, 1949 2,482,536 Hershberger et al. "1 Sept. 20, 1949 FOREIGN PATENTS Number Country Date 560,716 Great Britain Apr. 18, 1944 

1.AN IMPROVED BITUMINOUS BONDING COMPOSITION COMPRISING A MIXTURE OF ASPHALT AND AT LEAST ONE ANTI-STRIPPING ADDITION AGENT SELECTED FROM THE GROUP CONSISTING OF THE FREE AMINE BASE AND SALTS OF THE FREE AMINE BASE OF THE CONDENSATION PRODUCT OF ETHYLENE DIAMINE AND AN ALKYLTHIO SUBSTITUTED ALKYL HALIDE, SAID ALKYLTHIO, SUBSTITUTED ALKYL HALIDE CONTAINING ONLY CARBON, HYDROGEN, OXYGEN, SULFUR AND HALOGEN ELEMENTS, AND HAVING AN ALKYL RADICAL OF 10 TO 24 CARBON ATOMS. 